Blooming type compositions containing biphenyl solvents

ABSTRACT

Aqueous concentrated liquid hard surface cleaning compositions which bloom when added to a larger volume of water comprise: an organic solvent constituent; binary co-solvent system comprising an alkyl diphenyl solvent and a co-solvent; an amine oxide surfactant constituent; optionally, a further detersive surfactant constituent; and optionally, but desirably, at least one optional constituent selected from chelating agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, and pH buffers.

BACKGROUND OF THE INVENTION

The present invention relates to blooming type hard surface cleaningcompositions. More particularly the present invention relates toconcentrated liquid compositions which are normally diluted in a largervolume of water to form a working solution therefrom, and which exhibita blooming effect when diluted.

Blooming is a property exhibited by dilutable compositions such as knowncleaning compositions, specifically pine-oil type cleaning compositionswhich contain a significant amount (generally at least about 5% andmore) of pine oil. Certain phenolic disinfectant compounds, such asLYSOL(RTM) (where “RTM” indicates a proprietary tradename or trademark)disinfectant concentrate (Reckitt & Colman, Inc., Montvale N.J.) alsoexhibit such a blooming property. Blooming may be characterized as theformation of milky, creamy or cloudy appearance which is manifested whena dilutable composition is added to a larger volume or quantity ofwater. Such blooming is particularly desirable in compositions where theblooming characteristic in an aqueous dilution is long lasting.

SUMMARY OF THE INVENTION

Accordingly it is an object of the invention to provide an aqueousconcentrated liquid hard surface cleaning composition which blooms whenadded to a larger volume of water which comprises the followingconstituents:

an organic solvent constituent;

binary co-solvent system comprising an alkyl diphenyl solvent and aco-solvent;

an amine oxide surfactant constituent;

optionally, a further detersive surfactant constituent;

optionally but desirably at least one optional constituent selectedfrom: chelating agents, coloring agent, light stabilizers, fragrances,thickening agents, hydrotropes, pH adjusting agents, pH buffers, as wellas others known the art and useful in similar compositions. The one ormore optional constituents are selected to be present, and are includedin amounts which do not undesirably affect the overall bloomingcharacteristics of the present inventive compositions.

In preferred embodiments the concentrate compositions provide excellentinitial blooming characteristics in ‘as mixed’ dilutions with water.

It is a further object of the invention to provide such a concentratedliquid hard surface cleaning composition wherein the compositionexhibits a blooming effect when diluted in a larger volume of water.

It is among the further object of the invention to provide such aconcentrated liquid hard surface cleaning composition wherein thecomposition exhibits good long term stability, i.e., shelf stability inits concentrated form.

It is a further aspect of the invention to provide a process for thecleaning of hard surfaces utilizing the compositions in eitherconcentrated form or in diluted form as described herein.

DETAILED DISCLOSURE

Desirably, the inventive compositions are essentially free of terpenesolvents such as alpha-terpineols or d-limonene which are characteristicof products such as so-called “pine oil” cleaning compositions whichtypically include such terpene solvents.

The inventive compositions include an organic solvent constituent. Manyuseful organic solvents may be used, as long as it does not undesirablydisrupt the favorable characteristics of the invention, especially theblooming characteristic. Mixtures of two or more organic solvents mayalso be used as the organic solvent constituent.

Useful organic solvents are those which are at least parallywater-miscible such as alcohols, water-miscible ethers (e.g. diethyleneglycol diethylether, diethylene glycol dimethylether, propylene glycoldimethylether), water-miscible glycol ether (e.g. propylene glycolmonomethylether, propylene glycol mono ethylether, propylene glycolmonopropylether, propylene glycol monobutylether, ethylene glycolmonobutylether, dipropylene glycol monomethylether, diethyleneglycolmonobutylether), lower esters of monoalkylethers of ethyleneglycol orpropylene glycol (e.g. propylene glycol monomethyl ether acetate) allcommercially available from Union Carbide, Dow Chemicals or Hoescht.Mixtures of organic solvents can also be used.

Particularly useful organic solvents include glycols such as alkyleneglycols such as propylene glycol, and glycol ethers. Useful glycolethers are those having the general structure R_(a)—O—R_(b)—OH, whereinR_(a) is an alkyl of 1 to 20 carbon atoms, or an aryl of at least 6carbon atoms, and R_(b) is an alkylene of 1 to 8 carbons or is an etheror polyether containing from 2 to 20 carbon atoms. Examples of suchuseful glycol ethers include propylene glycol methyl ether, dipropyleneglycol methyl ether, tripropylene glycol methyl ether, propylene glycolisobutyl ether, ethylene glycol methyl ether, ethylene glycol ethylether, ethylene glycol butyl ether, diethylene glycol phenyl ether,propylene glycol phenol ether, and mixtures thereof. Preferred areethylene glycol n-butyl ether, diethylene glycol n-butyl ether, andmixtures thereof. Such glycol ethers are presently commerciallyavailable from a number of sources including in the DOWANOL™ glycolether from The Dow Chemical Company, Midland Mich. (USA).

Further particularly useful organic solvents monohydric (straightchained or branched) primary, secondary or tertiary lower aliphaticalcohols, especially C₁-C₆ aliphatic primary and secondary alcohols, ofwhich isopropanol is particularly preferred.

The present inventors have found that inclusion of the organic solventconstituent in amounts of about 0.001% by weight to about 50% by weighthave been found to be effective in providing effective cleaning,particularly when the compositions are dispersed into a larger volume ofwater, as well as in solubilizing other less water soluble constituentspresent in the concentrate compositions of the invention. Preferably,the organic solvent constituent is present in amounts of from 0.1-40% byweight, and most preferably from about 0.1-35% by weight.

Additionally the inventor has found the according to certain preferredembodiments the organic solvent constituent, comprises, and in certainespecially preferred embodiments consist essentially of, both analkylene glycol such as propylene glycol, and a monohydric loweraliphatic alcohol such as a C₁-C₆ aliphatic primary and secondaryalcohol, especially isopropyl alcohol.

The inventive compositions further also include a binary co-solventsystem comprising alkyl biphenyl solvent and a co-solvent which aids inthe solubilization of the biphenyl solvent in an aqueous medium.

The alkyl biphenyl solvent is one which may be generally represented bythe formula

wherein:

R₁ is hydrogen or is a lower alkyl radical, preferably a C₁-C₁₀, butmore preferably is a C₁-C₆ straight chained or branched alkyl radical,

R₂ is a lower alkyl radical, preferably a C₁-C₁₀, but more preferably isa C₁-C₆ straight chained or branched alkyl radical,

m is an integer from 1-3 inclusive; and,

n is an integer from 1-3 inclusive. Preferably R₁ is hydrogen, m is 1,and R₂ has any of the values indicated above. More preferably, R₁ ishydrogen and m is 1, and R₂ is a C₁-C₆ straight chained or branchedalkyl radical. It is to be understood that mixtures of the compoundsindicated above may be used as the biphenyl solvent constituent.

Such alkyl biphenyls are, per se, known to the art, and are described inU.S. Pat. No. 3,787,181. Particularly useful as the alkyl biphenylsolvent are materials presently marketed as NUSOLV(RTM) ABP solvents(Ridge Technologies Inc., Ridgewood N.J.) described to be a high purityalkyl biphenyls and mixtures thereof, and is also available from KochChemical Co. (Corpus Christi, Tex.) as SURESOL(RTM) solvents.

The alkyl biphenyl solvent may be present in the concentratecompositions in amounts of from about 0.001% by weight to up to about20% by weight, preferably about 0.01-10% by weight, most preferably inamount of between 0.1-8% by weight.

The inventors have observed that the concentrated compositions of theinvention are greatly improved with the addition of a co-solvent. Thisco-solvent aids in the solubilization of the alkyl biphenyl solvent inwater is desirably an at least partially water-niscible monohydricprimary alcohol, especially a water-miscible monohydric primary C₈-C₁₈alcohol. Particularly effective are cetyl, lauryl and myristyl alcohols,especially lauryl alcohols. The inventors have found that the inclusionof such alcohols greatly aids in the dissolution of the alkyl biphenylsolvents in the concentrate compositions according to the inventionbeing described herein, which aids in ensuring that clarity of theconcentrate composition is maintained which is particularly desirablefrom a consumer standpoint.

The co-solvent may be present in the concentrate compositions in amountsof from about 0.001% by weight to up to about 5% by weight, preferablyabout 0.01-3% by weight, most preferably in amount of between 0.1-2% byweight.

The concentrate compositions also include one or more amine oxidesurfactant constituents. Non-limiting examples of useful amine oxidesemi-polar nonionic surfactants include those according to the formulae:

wherein R₁ is hydrogen or is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl,or 3-alkoxy-2-hydroxypropyl radical where the alkyl and alkoxy partscontain from about 8 to about 18 carbon atoms, R₂ and R₃ areindependently selected from methyl, ethyl, propyl, isopropyl,2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, m is an integerfrom 2 to 4, and n is an integer from 0 to about 10. Preferably, theamine oxide semi-polar nonionic surfactants are those according to theformula immediately preceding wherein R₁ is an alkyl radical of from 12to 16 carbon atoms, R₂ and R₃ are independently selected from methyl orethyl, and n has a value of 0 or when n has a value of from 1-10, m hasa value of 2. Specific examples of such useful amine oxide semi-polarnonionic surfactants include cetyl-, myristyl- or lauryl-dimethyl amineoxide or mixtures thereof.

A further useful general class of useful amine oxides which may beincluded in the amine oxide constituent according to the invention arefurther alkyl di(lower alkyl)amine oxides in which the alkyl group hasabout 10-20, and preferably 12-16 carbon atoms, and can be straight orbranched chain, saturated or unsaturated. The lower alkyl groups includebetween 1 and 7 carbon atoms. Examples include those described above, aswell as those in which the alkyl group is a mixture of different amineoxides, dimethyl cocoamine oxides, dimethyl(hydrogenated tallow)amineoxides, and myristyl/palmityl dimethyl amine oxides.

A further class of useful amine oxides include alkyl di(hydroxy loweralkyl)amine oxides in which the alkyl group has about 10-20, andpreferably 12-16 carbon atoms, and can be straight or branched chain,saturated or unsaturated. Examples are bis(2-hydroxyethyl)cocoamineoxide, bis(2-hydroxyethyl)tallowamine oxide; andbis(2-hydroxyethyl)stearylamine oxide.

Further useful amine oxides include those which may be characterized asalkylamidopropyl di(lower alkyl)amine oxides in which the alkyl grouphas about 10-20, and preferably 12-16 carbon atoms, and can be straightor branched chain, saturated or unsaturated. Examples arecocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethylamine oxide; and

Additional useful amine oxides includes those which may be referred toas alkylmorpholine oxides in which the alkyl group has about 10-20, andpreferably 12-16 carbon atoms, and can be straight or branched chain,saturated or unsaturated.

Exemplary amine oxide surfactant constituents include AO-728(RTM) whichis described to be a composition containing 50% wt. ofbis-(2-hydroxyethyl C₁₂-C₁₅ alkyloxypropyl)amine oxide (Tomah ProductsInc., Milton Wis.), and AMMONYX(RTM) CDO Special described to becocoamidopropyl dimethyl amine (Stepan Co., Northfield Ill.).

The amine oxide constituent is present in the inventive concentratecompositions in amounts of up to 30% wt., preferably in amounts of from0.1-30% wt. and still more prefereably in amounts of from 1-20% wt., yetmore preferably 12-18% wt. and most preferably about 13-15% wt., basedon the total weight of the concentrate composition.

Water is added in order to provide 100% by weight of the concentratecomposition. Water is added in amounts which are sufficient to form theconcentrated compositions which amount is sufficient to ensure theretention of a substantially clear characteristic when produced as aconcentrate, but at the same time ensuring good blooming upon theaddition of the concentrated composition to a further amount of water,or upon the addition of further water to the concentrate. The water maybe tap water, but is preferably distilled and/or deionized water. If thewater is tap water, it is preferably appropriately filtered in order toremove any undesirable impurities such as organics or inorganics,especially minerals salts which are present in hard water which may thusinterfere with the operation of the other constituents of the invention,as well as any other optional components of the liquid concentratesaccording to the invention.

Other conventional additives known to the art but not expresslyenumerated here may also be included in the compositions according tothe invention. By way of non-limiting example without limitation thesemay include: chelating agents, coloring agents, light stabilizers,fragrances, thickening agents, hydrotropes, pH adjusting agents, pHbuffers as well as one or more detersive surfactants which do notdeleteriously detract from the blooming characteristics of the inventivecompositions. Many of these materials are known to the art, per se, andare described in McCutcheon's Detergents and Emulsifiers, North AmericanEdition, 1982; Kirk-Othmer, Encyclopedia of Chemical Technology, 3rdEd., Vol. 22, pp. 346-387, the contents of which are herein incorporatedby reference. Mixtures of two or more such surface active agents may beincorporated into the inventive compositions. Such optional, i.e.,non-essential constituents should be selected so to have little or nodetrimental effect upon the desirable characteristics of the presentinvention, namely the blooming behavior, cleaning efficacy, hard surfacecleaning activity, and low toxicity as provided by the inventivecompositions. Generally the total weight of such further conventionaladditives may comprise up to 20% by weight of a concentrated compositionformulation.

Further optional, but advantageously included constituents are one ormore coloring agents which find use in modifying the appearance of theconcentrate compositions and enhance their appearance from theperspective of a consumer or other end user. Known coloring agents, maybe incorporated in the compositions in effective amount to improve orimpart to concentrate compositions an appearance characteristic of apine oil type concentrate composition, such as a color ranging fromcolorless to a deep amber, deep amber yellow or deep amber reddishcolor. Such a coloring agent or coloring agents may be added in anyuseful amount in a conventional fashion, i.e., admixing to a concentratecomposition or blending with other constituents used to form aconcentrate composition. However, other colors atypical of pine oil typecleaning concentrates may be used as well. Known art light stabilizerconstituents useful in pine oil type compositions may also be added,particularly wherein coloring agents are used in a composition. As isknown to the art, such light stabilizers act to retain the appearancecharacteristics of the concentrate compositions over longer intervals oftime.

When a fragrance is included in a concentrate composition being taughtherein, the amount of such a fragrance is generally not in excess of0.5% wt., but is preferably even less, i.e., to 0.20% wt, but generallyeven less, i.e., to 0.10% wt. It is contemplated that this fragranceconstituent may include among its active agents terpene oils(alpha-terpenol, d-Limonene) which is included to provide a fragrancecharacteristic of a pine oil containing constituent. It is understoodthat such may be present in the inventive compositions as they may formpart of the fragrance constituent forming part of a concentratecomposition, but as they are present in only such small amounts they arenot considered to be part of a solvent constituent. However, it is notedthat the inventive compositions will function and exhibit satisfactoryblooming effect without such a fragrance constituent being present.

Exemplary useful buffers include the alkali metal phosphates,polyphospates, pyrophosphates, triphosphates, tetraphosphates,silicates, metasilicates, polysilicates, carbonates, hydroxides, andmixtures of the same. Certain salts, such as the alkaline earthphosphates, carbonates, hydroxides, can also function as buffers. It mayalso be suitable to use buffers such materials as aluminosilicates(zeolites), borates, aluminates and certain organic materials such asgluconates, succinates, maleates, and their alkali metal salts. Suchbuffers keep the pH ranges of the compositions of the present inventionwithin acceptable limits.

Exemplary useful pH adjusting agents include known materials which maybe used to adjust the pH of the concentrate compositions to a desiredrange.

The inventive compositions further include optionally, but in certainembodiments, desirably, one or more further detersive surfactants.Useful detersive surfactants include anionic, nonionic, cationic andamphoteric surfactants which are found to not undesirably detract fromthe blooming characteristics of the present invention.

The useful nonionic surfactants, include known art nonionic surfactantcompounds. Practically any hydrophobic compound having a carboxy,hydroxy, amido, or amino group with a free hydrogen attached to thenitrogen can be condensed with ethylene oxide or with the polyhydrationproduct thereof, polyethylene glycol, to form a water soluble nonionicsurfactant compound. Further, the length of the polyethylenoxyhydrophobic and hydrophilic elements may various. Exemplary nonioniccompounds include the polyoxyethylene ethers of alkyl aromatic hydroxycompounds, e.g., alkylated polyoxyethylene phenols, polyoxyethyleneethers of long chain aliphatic alcohols, the polyoxyethylene ethers ofhydrophobic propylene oxide polymers, and the higher alkyl amine oxides.

Exemplary useful nonionic surfactants in the compositions according tothe present invention include commercially well known surfactantcompositions.

Exemplary nonionic surfactants are certain ethoxylates presentlycommercially available under the trade name NEODOL(RTM) (Shell ChemicalCo., Houston, Tex.(USA)), which are ethoxylated higher aliphatic,primary alcohols Such ethoxylates have an HLB (hydrophobic to lipophilicbalance) value of about 8 to 15 and give good oil/water emulsification,whereas ethoxylates with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.Additional satisfactory nonionic surfactant compositions include thecondensation products of a secondary aliphatic alcohols containing 8 to18 carbon atoms in a straight or branched chain configuration condensedwith 5 to 30 moles of ethylene oxide. Examples of commercially availablenonionic detergents of the foregoing type are those presentlycommercially available under the trade name of TERGITOL(RTM) (UnionCarbide Co., Danbury, Conn.(USA)).

Other suitable nonionic surfactant compositions include the polyethyleneoxide condensates of one mole of alkyl phenol containing from about 8 to18 carbon atoms in a straight- or branched chain alkyl group with about5 to 30 moles of ethylene oxide, including those which are presentlycommercially available under the trade name of IGEPAL(RTM)(Rhône-Poulenc, Princeton N.J.(USA)). Further useful nonionicsurfactants include the water-soluble condensation products of a C₈-C₂₀alkanol with a mixture of ethylene oxide and propylene oxide wherein theweight ratio or ethylene oxide to propylene oxide is from 2.5:1 to 4:1,preferably 2.89:1 to 3.3:1, with the total of the ethylene oxide; andpropylene oxide (including the terminal ethanol or proponol group) beingfrom 60-85%, preferably 70 to 80%, by weight. Such include thosecommercially available under the trade name of PLURAFAC(RTM) (BASFCorp., Hackettstown, N.J. (USA)). Still further useful water-solublenonionic surfactants include condensation products of a C₈-C₂₀ alkanolswith a mixture of ethylene oxide and/or propylene oxide. Such arecommercially available under the tradenarne POLYTERGENT(RTM) (OlinChemical Co., Stamford Conn.(USA)).

Further suitable water-soluble nonionic surfactants which may also beused include those which are marketed under the trade namePLURONICS(RTM) (BASF Corp., Hackettstown, N.J. (USA)). These are formedby condensing ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol. Further usefulnonionic surfactants include Alkylmonoglyocosides andalkylpolyglycosides which are alkaline and electrolyte stable. Such areprepared generally by reacting a monosaccharide, or a compoundhydrolyzable to a monosaccharide with an alcohol such as a fatty alcoholin an acid medium. Various glycoside and polyglycoside compoundsincluding alkoxylated glycosides may be used. An exemplary usefulpolyglycoside is one according to the formula:

R₂O—(C_(n)H_(2n)O)_(w)—(Z)_(x)

where Z is derived from glucose, R is a hydrophobic group selected fromalkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well asmixtures thereof, wherein the alkyl groups may be straight chained orbranched, which contain from about 8 to about 18 carbon atoms, n is 2 or3, w is an integer from 0 to 10, but is preferably 0, and x is a valuefrom about 1 to 8, preferably from about 1.5 to 5. Preferably thealkylpolyglycosides are nonionic fatty alkylpolyglucosides which containa straight chain or branched chain C₈-C₁₅ alkyl group, and have anaverage of from about 1 to about 5 glucose units per fattyalkcylpolyglucoside molecule. More preferably, the nonionic fattyalkylpolyglucosides which contain straight chain or branched C₈-C₁₅alkyl group, and have an average of from about 1 to about 2 glucoseunits per fatty alkylpolyglucoside molecule.

A further exemplary group of alkyl glycoside surfactants suitable foruse in the practice of this invention may be represented by formula Ibelow:

RO—(R₁O)_(y)—(G)_(x)Z_(b)

wherein: R is a monovalent organic radical containing from about 6 toabout 30, preferably from about 8 to about 18 carbon atoms; R₁ is adivalent hydrocarbon radical containing from about 2 to about 4 carbonatoms; O is an oxygen atom;

y is a number which has an average value from about 0 to about 1 and ispreferably 0; G is a moiety derived from a reducing saccharidecontaining 5 or 6 carbon atoms; and x is a number having an averagevalue from about 1 to 5 (preferably from 1.1 to 2);

Z is O₂M¹,

O(CH₂), CO₂M¹, OSO₃M¹, or O(CH₂)SO₃M¹; R₂ is (CH₂)CO₂M¹ or CH═CHCO₂M¹;(with the proviso that Z can be O₂M¹ only if Z is in place of a primaryhydroxyl group in which the primary hydroxyl-bearing carbon atom,—CH₂OH, is oxidized to form a

 group); b is a number of from 0 to 3x+1 preferably an average of from0.5 to 2 per glycosal group; p is 1 to 10, M¹ is H⁺ or an organic orinorganic counterion, particularly cations such as, for example, analkali metal cation, ammonium cation, monoethanolamine cation, orcalcium cation.

As defined in Formula I above, R is generally the residue of a fattyalcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms.Examples of such alkylglycosides as described above include, forexample, APG™ 325 CS Glycoside® which is described as being a 50% C₉-C₁₁alkyl polyglycoside, also commonly referred to as D-glucopyranoside,(commercially available from Henkel Corp, Ambler Pa.) and Glucopon™ 625CS which is described as being a 50% C₁₀-C₁₆ alkyl polyglycoside, alsocommonly referred to as a D-glucopyranoside, (available from HenkelCorp., Ambler Pa.).

Further exemplary useful nonionic surfactants which may be used includecertain alkanolamides including monoethanolamides and diethanolamides,particularly fatty mionoalkanolamides and fatty dialkanolamides.Commercially available monoethanol amides and diethanol amides includethose marketed under the trade names ALKAMIDE® and CYCLOMIDE® byRhône-Poulenc Co., (Cranbury, N.J.).

The nonionic surfactants, when present, can be present either singly, oras a mixture of two or more nonionic surfactant compounds as definedabove.

Exemplary anionic surfactants include compounds known to the art asuseful as anionic surfactants. These include but are not limited to:alkali metal salts, ammonium salts, amine salts, aminoalcohol salts orthe magnesium salts of one or more of the following compounds: alkylsulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates,alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkylphosphates, alkyl ether phosphates, acyl sarcosinates, acylisethionates, and N-acyl taurates. Generally, the alkyl or acyl radicalin these various compounds comprise a carbon chain containing 12 to 20carbon atoms.

Further exemplary anionic surface active agents which may be usedinclude fatty acid salts, including salts of oleic, ricinoleic,palmitic, and stearic acids; copra oils or hydrogenated copra oil acid,and acyl lactylates whose acyl radical contains 8 to 20 carbon atoms.

More specific examples of suitable alkyl aromatic sulfonate detergentsinclude the straight chain linear alkyl benzene sulfonates wherein thealkyl group contains 10 to 18 carbon atoms, e.g., averaging about 10 to15, specific examples of which are sodium dodecyl benzene sulfonate,sodium tridecyl benzene sulfonate and sodium higher alkyl benzenesulfonate wherein the alkyl is of 10 to 15 carbon atoms, averaging about12.5 carbon atoms per molecular proportion.

Other suitable agents are the surface-active sulfated or sulfonatedaliphatic compounds, preferably of 12 to 22 carbon atoms. Within thescope of such definition are the sulfuric acid esters of polyhydricalcohols incompletely esterified with higher fatty acids, e.g., coconutoil monoglyceride monosulfate, tallow diglyceride monosulfate; the longchain pure or mixed alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate;the hydroxysulfonated higher fatty acid esters, such as the higher fattyacid esters of low molecular weight alkyl sulfonic acids, e.g., fattyacid esters of isethionic acid; the fatty acid ethanolamide sulfates;the fatty acid amides of aminoalkyl sulfonic acids, e.g., the lauricacid amide of taurine; olefin and paraffin sulfonates; and the like.More particularly, it is preferred to use the sulfated aliphaticcompounds containing at least about 8 carbon atoms, especially thosehaving about 12 to about 18 or 22 carbon atoms in the molecule.

Preferred to use the aliphatic sulfates and sulfonates of about 8 to 22carbon atoms and the alkyl aromatic sulfonates containing about 8 toabout 22 carbon atoms in the alkyl group, preferably of 12 to 18 carbonatoms.

For the synthetic anionic compounds, the alkali metal (e.g., sodium,potassium) salts are preferred, although other salts such as ammonium,lower alkyl amine, i.e., straight or branched chain mono-, di andtrialkylamines of 1 to 4 carbons in the alkyl group e.g., methyl aminediisopropyl amine and tributyl amine; lower alkanolamine, e.g.,ethanolamine, diethanolamine, triethanolamine and isopropanolamine; andalkaline earth and similar metal, e.g., calcium and magnesium salts; maybe used, if desired.

Further exemplary useful anionic surface active agents include alkylether carboxylates, particularly those having the general structuralformula:

R—O—(C_(n)H_(2n)O)_(m)—R₁—COO⁻M⁺

wherein R is a straight or branched, long chain, alkyl group containingfrom 8 to 18 carbon atoms, n is an integer from 2 to 4, m is an integerfrom 1 to 100, R₁ is CH₂, CH₂CH₂, or CH₂CH₂CH₂, and M is a counterionsuch as an organic or inorganic cation including singly valent cationsas well as polyvalent cations. Exemplary cations include cations of analkali metal including sodium or lithium, or organic cations such asammonium, diethylammonium, or trimethylammonium cations, as well asother cations not particulary recited here. Such anionic alkyl ethercarboxylates are known to be useful as surfactant compositions. In thecompositions according to the instant invention, preferably n is 2, m is4-11, R is C₉-C₁₆, R₁ is CH₂ and M is the cation of an alkali metal,preferably sodium. Such surfactants are presently commercially availableunder the trade name SANDOPAN(RTM) (Clariant Chemical Corp., CharlotteN.C.), NEODOX(RTM) 25-6 and NEODOX(RTM) 23-4 (Shell Chemical Co.,Houston, Tex.), as well as SURFINE(RTM) WLG(Finetex Inc., Elmwood Park,N.J.).

Other anionic surface active agents not particularly enumerated here mayalso find use in conjunction with the compounds of the presentinvention.

One class of particularly useful detersive surfactants are polymericalkylene oxide block copolymer. Polymeric alkylene oxide blockcopolymers include nonionic surfactants in which the major portion ofthe molecule is made up of block polymeric C₂-C₄ alkylene oxides. Suchnonionic surfactants, while preferably built up from an alkylene oxidechain starting group, and can have as a starting nucleus almost anyactive hydrogen containing group including, without limitation, amides,phenols, thiols and secondary alcohols.

One group of such useful nonionic surfactants containing thecharacteristic alkylene oxide blocks are those which may be generallyrepresented by the formula (A):

HO—(EO)_(x)(PO)_(y)(EO)_(z)—H  (A

where

EO represents ethylene oxide,

PO represents propylene oxide,

y equals at least 15,

(EO)_(x+z) equals 20 to 50% of the total weight of said compounds, and,the total molecular weight is preferably in the range of about 2000 to15,000.

Another group of nonionic surfactants appropriate for use in the newcompositions can be represented by the formula (B):

R—(EO,PO)_(a)(EO,PO)_(b)—H  (B

wherein R is an alkyl, aryl or aralkyl group, where the R group contains1 to 20 carbon atoms, the weight percent of EO is within the range of 0to 45% in one of the blocks a, b, and within the range of 60 to 100% inthe other of the blocks a, b, and the total number of moles of combinedEO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in thePO rich block and 5 to 100 moles in the EO rich block.

Further nonionic surfactants which in general are encompassed by FormulaB include butoxy derivatives of propylene oxide/ethylene oxide blockpolymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy(BO) groups can be represented by formula (C) as follows:

RO—(BO)_(n)(EO)_(x)—H  (C

wherein

R is an alkyl group containing 1 to 20 carbon atoms,

n is about 5-15 and x is about 5-15.

Also useful as the nonionic block copolymer surfactants, which alsoinclude polymeric butoxy groups, are those which may be represented bythe following formula (D):

HO—(EO)_(x)(BO)_(n)(EO)_(y)—H  (D)

wherein

n is about 5-15, preferably about 15,

x is about 5-15, preferably about 15, and

y is about 5-15, preferably about 15.

Still further useful nonionic block copolymer surfactants includeethoxylated derivatives of propoxylated ethylene diamine, which may berepresented by the following formula:

where

(EO) represents ethoxy,

(PO) represents propoxy,

the amount of (PO)_(x) is such as to provide a molecular weight prior toethoxylation of about 300 to 7500, and the amount of (EO)_(y) is such asto provide about 20% to 90% of the total weight of said compound.

Of these, the most preferred are those which are represented by formula(A) above; specific examples of which include those materials presentlycommercially available under the tradename PLURONIC(RTM), and inparticular the F, L, P, and R serieseach of which are generallydescribed to be block copolymers of propylene oxide and ethylene oxide.Generally those of the PLURONIC(RTM) L series and the PLURONIC(RTM) Rseries are preferred as these are supplied in liquid form by themanufacturer and are readily formulated into the present inventivecompositions. These are also available in a wide range of HLB values,and those having HLB values in the range of 1.0-23.0 may be used,although those with intermediate HLB values such as from about 12.0-18.0are found to be particularly advantageous. These materials are presentlycommercially available from BASF AG (Ludwigshafen, Germany) as well asfrom BASF Corp. (Mt. Olive Township, N.J.).

Other useful exemplary nonionic block copolymers based on a polymericethoxy/propoxy units which may also be used include those presentlycommercially available in the POLYTERGENT(RTM), series of materials fromOlin Chemicals Corp., (Stamford Conn.). These are described to benonionic surfactants based on ethoxy/propoxy block copolymers,conveniently available in a liquid form from its supplier. It is to beunderstood that these nonionic surfactants based on polymeric alkyleneoxide block copolymers may be used singly or in mixtures of two or moresuch compounds.

Exemplary cationic surface active agents include, by way of non-limitingexample, include those which include charged nitrogen containingcompounds such as quaternary ammonium compounds, as well as others knownto the art. An exemplary and preferred cationic compound quaternaryammonium compounds and salts thereof, which may be characterized by thegeneral structural formula:

where at least one of R₁, R₂, R₃ and R₄ is a alkyl, aryl or alkylarylsubstituent of from 6 to 26 carbon atoms, and the entire cation portionof the molecule has a molecular weight of at least 165. The alkylsubstituents may be long-chain alkyl, long-chain alkoxyaryl, long-chainalkylaryl, halogen-substituted long-chain alkylaryl, long-chainalkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on thenitrogen atoms other than the abovementioned alkyl substituents arehydrocarbons usually containing no more than 12 carbon atoms. Thesubstituents R₁, R₂, R₃ and R₄ may be straight-chained or may bebranched, but are preferably straight-chained, and may include one ormore amide, ether or ester linkages. The counterion X may be anysalt-forming anion which permits water solubility of the quaternaryammonium complex. Certain of these quaternary ammonium compounds mayexhibit a germicidal effect, but this is not essential to the presentinvention.

Exemplary anphoteric surface active agents include, by way ofnon-limiting example, one or more further known art surfactantcompositions, including betaines, ethylene oxide condensates, and fattyacid amides.

Exemplary useful betaine surfactants include those according to thegeneral formula:

wherein R is a hydrophobic group selected from the group consisting ofalkyl groups containing from about 10 to about 22 carbon atoms,preferably from about 12 to about 18 carbon atoms, alkyl aryl, and arylalkyl groups containing a similar number of carbon atoms with a benzenering being treated as equivalent to about 2 carbon atoms, and similarstructures interrupted by amido or ether linkages; each R₁ is an alkylgroup containing from 1 to about 3 carbon atoms; and R₂ is an alkylenegroup containing from 1 to about 6 carbon atoms.

Examples of preferred betaines are dodecyl dimethyl betaine, cetyldimethyl betaine, dodecyl amidopropyldimethyl betaine,tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, anddodecyldimethylammnonium hexanoate.

Useful fatty acid amides include those which are known to the art.Particular exemplary fatty acid amide surfactants include ammonia,monoethanol, and diethanol amides of fatty acids having an acyl moietywhich contains from about 8 to about 18 carbon atoms, and which may berepresented in accordance with the formula:

R₁—CO—N(H)_(m−1)(R₂OH)_(3−m)

where R₁ represents a saturated or unsaturated aliphatic hydrocarbonradical of from about 7 to 21 carbon atoms, but preferably from about 11to 17 carbon atoms; R₂ represents a —CH₂— or —CH₂CH₂—, and m is aninteger from 1 to 3, but is preferably 1. Preferably, R₁ is a saturatedor unsaturated aliphatic hydrocarbon radical comprising from about 11 to17 carbon atoms, and m is 1.

Further examples of such compounds include mono-ethanol amine coconutfatty acid amide and diethanol amine dodecyl fatty acid amide. Anexemplary useful fatty acid amide includes cocomonoethanol amide orcocodiethanolamide, which are presently commercially available asMONAMID(RTM) CMA (Mona Industries, Paterson N.J. (USA)).

What is to be understood by the term “concentrate” and “concentratecomposition” in this specification and claims is the pre-consumerdilution and composition of the cleaning composition which is theessentially the form of the product prepared for sale to the consumer orother end user. Such a consumer or other end user would then normally beexpected to dilute the same with water to form a cleaning composition.It is to be understood however that nothing in this invention would barits use as cleaning composition without any further dilution and it maybe used in the concentrations in which it was prepared for sale.Similarly, what is to be understood by the term “cleaning compositions”are the water diluted compositions which are expected to be prepared bythe consumer or other end user by mixing a measured amount of the“concentrate” with water in order to form an appropriately dilutedcleaning composition which is suitable for use in cleaning applications,especially in the cleaning of hard surfaces.

It is also to be understood, that proportions of one or moreconstituents have been and generally are referred to as percent byweight or as parts by weight based on a measure of 100% by weight,unless otherwise indicated.

According to certain particularly preferred embodiments of the inventionthere are provided object of the invention to provide an aqueousconcentrated liquid hard surface cleaning composition which blooms whenadded to a larger volume of water which comprises the followingconstituents:

0.1-35% wt. of an organic solvent constituent;

0.1-12% wt. of a binary co-solvent system comprising an alkyl diphenylsolvent and a co-solvent;

1-20% wt. an amine oxide surfactant constituent;

1-10% wt. of at least one further detersive surfactant constituent;

0-20% wt. of at least one optional constituent selected from: chelatingagents, coloring agent, light stabilizers, fragrances, thickeningagents, hydrotropes, pH adjusting agents, pH buffers

As generally denoted above, the formulations according to the inventioninclude both cleaning compositions and concentrates as outlined abovewhich differ only in the relative proportion of water to that of theother constituents forming such formulations. While the concentratedform of the cleaning compositions find use in their original form, theyare more frequently used in the formation of a cleaning compositiontherefrom. Such may be easily prepared by diluting measured amounts ofthe concentrate compositions in water by the consumer or other end userin certain weight ratios of concentrate:water, and optionally, agitatingthe same to ensure even distribution of the concentrate in the water. Asnoted, the concentrate may be used without dilution, i.e., inconcentrate:water concentrations of 1:0, to extremely dilute dilutionssuch as 1:10,000. Desirably, the concentrate is diluted in the range of1:0.1-1:1000, preferably in the range of 1:1-1:500 but most preferablyin the range of 1:10-1:100. The actual dilution selected is in partdeterminable by the degree and amount of dirt and grime to be removedfrom a surface(s), the amount of mechanical force imparted to remove thesame, as well as the observed efficacy of a particular dilution.Generally better results and faster removal is to be expected at lowerrelative dilutions of the concentrate in water.

In accordance with preferred embodiments of the invention, when aquantity of the concentrate compositions taught herein are added to alarger volume of water, a blooming characteristic is manifested. Such“blooming” may be broadly characterized as the formation of milky,creamy or cloudy appearance which is manifested when a dilutablecomposition is added to a larger volume or quantity of water. Such“blooming” may be alternately characterized as the reduction oftransmitted light through an amount of water by at least 30%, desirablyby at least 40%, yet more desirably by at least about 50%, and yet mostdesirably by at least 60% or more when a dilution of the concentratecomposition:water with the weight or volume ratio range of from 1:64 to1:102 is formed. That such blooming may be attained without the use ofpine oil fractions as is common in certain commercially available pineoil containing preparations is surprising.

As has been noted, concentrate compositions according to preferredembodiments of the invention exhibit a long lasting blooming effect whenthey are diluted into a larger volume of water, especially when used toform (weight ratio) dilutions with water of concentrate:water of 1:64 atroom temperature. Desirably, such dilutions do not exhibit an increasein light transmittance in accordance with the measurement methodsdiscussed in the Examples below, of more than 50% (based on the initial‘as mixed’ value) during its initial three-day interval.

The concentrate compositions according to the invention, and aqueousdilutions formed therefrom, are particularly useful in the cleaning ofhard surfaces. By way of non-limiting example, hard surfaces includesurfaces composed of refractory materials such as: glazed and unglazedtile, brick, porcelain, ceramics as well as stone including marble,granite, and other stones surfaces; glass; metals; plastics e.g.polyester, vinyl; fiberglass, FORMICA(RTM), CORIAN(RTM) and other hardsurfaces known to the art. Hard surfaces which are to be particularlydenoted include those associated with kitchen environments, lavatoryenvironments, especially flooring surfaces and the surfaces of fixtures(doors, cabinets, shelving, and the like) in such environments.

Such dilution ratios of concentrate:water as described above may bevolume/volume basis, or a weight/weight basis.

The following examples below illustrate exemplary and among them,preferred formulations of the composition according to the instantinvention. It is to be understood that these examples are presented bymeans of illustration only and that further useful formulations fallwithin the scope of this invention and the claims may be readilyproduced by one skilled in the art and not deviate from the scope andspirit of the invention.

TABLE 1 Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8 Isopropyl alcohol 12.0012.00 12.00 12.00 12.00 12.00 12.00 12.00 propylene glycol 20.00 20.0020.00 20.00 20.00 20.00 20.00 20.00 lauryl alcohol 1.00 1.00 1.00 1.001.00 1.00 1.00 1.00 NUSOLV(RTM) ABP-103 2.50 2.50 2.50 2.50 2.50 2.252.25 2.25 TOMAH(RTM) AO-728 14.00 14.00 14.00 14.00 14.00 14.00 14.0014.00 Special Na₂EDTA — — — 0.50 — — — — SANDOPAN(RTM) LS-24 0.73 — — —— — — — TERGITOL(RTM) 15-S-9 — 0.5 — — — — — — PLURONIC(RTM) L64 — — 0.5— — — — — STEOL(RTM) 4N — — — — — 1.79 — — BIOSOFT(RTM) D-40 — — — — — —1.32 — STEPANATE(RTM) SXS — — — — — — — 1.25 di water q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s.

The individual constituents were used “as supplied” from theirrespective manufacturer, and the percent actives of individualconstituents are 100% unless otherwise indicated. All of theformulations on Table 1 indicate their constituents in weight percent.

The identity of the constituents indicated on Table 1 are indicated onthe following table.

TABLE 2 NUSOLV(RTM) ABP-103 technical grade mixture of alkyl biphenyls(100% wt. actives) from Arristec Inc. TOMAH(RTM) AO-728bis-2-hydroxyethyl C₁₂-C₁₅ alkyloxypropyl) Special amine oxide (50% wt.actives) from Tomah Products Co. SANDOPAN(RTM) LS-24 sodium lauryl ethercarboxylate, (69% wt. actives) from Clariant Inc. TERGITOL(RTM) 15-S-9secondary alcohol ethoxylate (100% wt. actives) STEOL(RTM) 4N sodiumlaureth sulfate, also known as sodium lauryl ether sulfate (28% actives)from Stepan Co. PLURONIC(RTM) L64 block copolymer of ethyleneoxide/propylene oxide (100% wt. actives) from BASF Inc. BIOSOFT(RTM)D-40 linear sodium alkyl benzene sulfonate (38% actives) from Stepan Co.STEPANATE(RTM) SXS sodium xylene sulfonate (40% actives) from Stepan Co.Na₂EDTA disodium salt of ethylenediaminetetraacetic acid (100% wt.actives) di water deionized water

The blooming characteristics of these formulations was characterized byusing the Brinkman Sybron (RTM) PC 801 colorimeter. Each testedformulation were diluted with deionised water in a weight ratio of 1:64,and the test was carried out with each of the formulations and water atroom temperature (68° F., 20° C.). The resulting determined values,reported as “blooming” in the following table provide an empiricalevaluation in percent transmittance (%) of the degree of transparency ofa diluted example formulation wherein 0% indicates complete opacity and100% the transparency of a deionised water sample. The result wastabulated as follows:

TABLE 2 % Transmittance Ex. 1 33.4 Ex. 2 29.3 Ex. 3 30.7 Ex. 4 21.5 Ex.5 24.4 Ex. 6 30.9 Ex. 7 19.2 Ex. 8 20.3

Cleaning Test

The compositions described on Table 1 provide good cleaning efficacyboth in their as-mixed, concentrated form, and diluted in water in aweight ratio of 1:64.

What is claimed is:
 1. An aqueous concentrated liquid hard surfacecleaning composition which blooms when added to a larger volume ofwater, said composition comprising: an organic solvent constituent; abinary co-solvent system comprising an alkyl diphenyl solvent and atleast one co-solvent; and an amine oxide surfactant constituent, whichcomposition is essentially free of terpene solvents.
 2. A cleaningcomposition according to claim 1 wherein the alkyl diphenyl solvent is acompound of the formula

wherein R₁ is hydrogen or a C₁-C₁₀ lower alkyl radical, R₂ is hydrogenor a C₁-C₁₀ lower alkyl radical, m is an integer from 1 to 3, and n isan integer from 1 to
 3. 3. A cleaning composition according to claim 2wherein R₁ is hydrogen or a C₁-C₆ straight chain or branched alkylradical, and R₂ is a C₁-C₆ straight chain or branched alkyl radical. 4.A cleaning composition according to claim 3 wherein R₁ is a C₁-C₆straight chained or branched alkyl radical.
 5. A cleaning compositionaccording to claim 3 wherein R₁ is hydrogen, and m is
 1. 6. A cleaningcomposition according to claim 1 wherein the organic solvent constituentis selected from the group consisting of water-miscible alcohols,ethers, glycol ethers, lower esters of monoalkyl ethers of ethyleneglycol or propylene glycol, and mixtures thereof.
 7. A cleaningcompositions according to claim 1 wherein the organic solventconstituent comprises propylene glycol.
 8. A cleaning compositionaccording to claim 6 wherein the organic solvent constituent comprises aglycol ether of the formula R_(a)—O—R_(b)—OH wherein R_(a) is a C₁-C₂₀alkyl radical or an aryl of at least 6 carbon atoms, and R_(b) is aC₁-C₈ alkylene radical or is an ether or polyether having from 2 to 20carbon atoms.
 9. A cleaning composition according to claim 8 wherein theorganic solvent constituent comprises propylene glycol methyl ether,dipropylene glycol methyl ether, tripropylene glycol methyl ether,propylene glycol isobutyl ether, ethylene glycol methyl ether, ethyleneglycol ethyl ether, ethylene glycol butyl ether, diethylene glycolphenyl ether or propylene glycol phenol ether.
 10. A cleaningcomposition according to claim 9 wherein the organic solvent constituentis ethylene glycol n-butyl ether, diethylene glycol n-butyl ether or amixture thereof.
 11. A cleaning composition according to claim 6 whereinthe organic solvent constituent comprises a monohydric C₁-C₆ primary orsecondary alcohol.
 12. A cleaning composition according to claim 11wherein the organic solvent constituent is isopropanol.
 13. A cleaningcomposition according to claim 2 wherein the co-solvent comprises one ormore monohydric C₈-C₁₈ primary alcohols.
 14. A cleaning compositionaccording to claim 13 wherein the co-solvent is lauryl alcohol, myristylalcohol, cetyl alcohol or mixtures thereof.
 15. A cleaning compositionaccording to claim 14 wherein the co-solvent is lauryl alcohol.
 16. Acleaning composition according to claim 1 which comprises one or moreamine oxide surfactants of the formula:

wherein R₁ is hydrogen or an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or3-alkoxy-2-hydroxypropyl radical where the alkyl and alkoxy groupscontain from about 8 to about 18 carbon atoms, R₂ and R₃ areindependently selected from methyl, ethyl, propyl, isopropyl,2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, m is an integerfrom 2 to 4, and n is an integer from 0 to
 10. 17. A cleaningcomposition according to claim 16 wherein R₁ is an alkyl of from 12 to16 carbon atoms, R₂ and R₃ are independently selected from methyl andethyl; m is 2, and n is an integer of from 1 to
 10. 18. A cleaningcomposition according to claim 16 wherein the amine oxide is selectedfrom cetyl- myristyl- or lauryl-dimethyl amine oxides, mixtures thereof,dimethyl cocoamine oxides, dimethyl (hydrogenated tallow) amine oxidesand myristyl/palmityl-dimethyl amine oxides.
 19. A cleaning compositionaccording to claim 16 wherein wherein R₁ is an alkyl of from 12 to 15carbon atoms, each of R₂ and R₃ is 2-hydroxyethyl, and n is
 0. 20. Acleaning composition according to claim 19 wherein the amine oxide isselected from bis(2-hydroxyethyl)-cocoamine oxide,bis(2-hydroxyethyl)-tallowamine oxide andbis(2-hydroxyethyl)-stearylamine oxide.
 21. A cleaning compositionaccording to claim 16 wherein the amine oxide constituent comprisesbis(2-hydroxyethyl)-(C₁₂-C₁₅ alkoxypropyl)-amine oxide.
 22. A cleaningcomposition according to claim 1 wherein the amine oxide constituentcomprises an alkylamido-propyldimethylamine in which the alkyl group hasfrom about 10 to about 20 carbon atoms.
 23. A cleaning compositionaccording to claim 22 wherein the amine oxide is cocoamidopropyldimethylamine oxide or tallowamidopropyldimethylamine oxide.
 24. A cleaningcomposition according to claim 1 wherein the amine oxide constituentcomprises an alkylmorpholine oxide in which the alkyl group has from 10to 20 carbon atoms.
 25. A cleaning composition according to claim 1which additionally comprises a further detersive surfactant constituentselected from the group consisting of non-ionic, anionic, cationic andamphoteric surfactants and mixtures thereof.
 26. A cleaning compositionaccording to claim 25 in which the further detersive surfactantconstituent comprises an alkyl ether carboxylate.
 27. A cleaningcomposition according to claim 25 in which the further detersivesurfactant constituent comprises an ethylene oxide/propylene oxidesurfactant.
 28. A cleaning composition according to claim 25 in whichthe further detersive surfactant constituent comprises an alcoholethoxylate.
 29. A cleaning composition according to claim 25 in whichthe further detersive surfactant constituent comprises an alkyl sulfate.30. A cleaning composition according to claim 25 in which the furtherdetersive surfactant constituent comprises an alkyl sulfonate.
 31. Acleaning composition according to claim 25 in which the furtherdetersive surfactant constituent comprises an alkyl benzene sulfonate.32. A cleaning composition according to claim 1 which includes one ormore additional constituents selected from the group consisting ofchelating agents, coloring agents, light stabilizers, fragrances,thickening agents, hydrotropes, pH adjusting agents and pH buffers. 33.An aqueous concentrated liquid hard surface cleaning composition whichcomprises: 0.1-35% wt. of an organic solvent constituent; 0.1-10% wt. ofa binary co-solvent system comprising an alkyl diphenyl solvent and aco-solvent; 1-20% wt of an amine oxide surfactant constituent; 0.1-10%wt. of at least one further detersive surfactant constituent; 0-20% wt.of at least one optional constituent selected from the group consistingof chelating agents, coloring agents, light stabilizers, fragrances,thickening agents, hydrotropes, pH adjusting agents and pH buffers. 34.A cleaning composition according to claim 33 which blooms when dilutedat a 1:64 v/v ratio in room temperature water.
 35. A method for cleaninga hard surface which comprises the step of contacting the hard surfacewith an aqueous liquid hard surface cleaning composition comprising:0.1-35% wt. of an organic solvent constituent; 0.1-10% wt. of a binaryco-solvent system comprising an alkyl diphenyl solvent and a co-solvent;1-20% wt. of an amine oxide surfactant constituent; 0.1-10% wt. of atleast one further detersive surfactant constituent; and 0-20% wt. of atleast one optional constituent selected from the group consisting ofchelating agents, coloring agents, light stabilizers, fragrances,thickening agents, hydrotropes, pH adjusting agents and pH buffers, saidcomposition being diluted to a ratio of from 1:64 to 1:102.